Piperonyl ethers having juvenile hormone mimetic activity

ABSTRACT

COMPOUND OF THE FORMULA   5-(R-(CH2)N-O-CH2-)-1,3-BENZODIOXOLE   WHEREIN R IS HYDROGEN, HALOGEN OF ATOMIC NUMBER 9 TO 35 VINYL, ALKOXY GROUP OF 1 TO 4 CARBON ATOMS, ALKYLTHIO GROUP OF 1 TO 4 CARBON ATOMS, EPOXY GROUP, ACYL GROUP OR CARBAMOLY GROUP SINGLY SUBSTITUTED ON THE NITROGEN ATOM WITH AN ALKYL GROUP OF 1 TO 4 CARBON ATOMS AND N IS A WHOLE NUMBER IN THE RANGE OF 1 TO 14, HAVE JUVENILE HORMONE MIMETIC ACTIVITY.

nited States Patent O 3,796,726 PIPERONYL ETHERS HAVING JUVENILE HORMONEMIMETIC ACTIVITY Laroy H. Edwards, Napa, Califi, assignor to ChevronResearch Company, San Francisco, Calif. No Drawing. Filed Feb. 16, 1972,Ser. No. 226,963 Int. Cl. C07d 13/10 US. Cl. 260-3405 11 Claims ABSTRACTOF THE DISCLOSURE Compound of the formula wherein R is hydroxy, halogenof atomic number 9 to 35, vinyl, alkoxy group of 1 to 4 carbon atoms,alkylthio group of 1 to 4 carbon atoms, epoxy group, acyl group orcarbamoyl group singly substituted on the nitrogen atom with an alkylgroup of 1 to 4 carbon atoms and n is a whole number in the range of 1to 14, have juvenile hormone mimetic activity.

BACKGROUND OF THE INVENTION Field The present invention is concernedwith piperonyl others that have juvenile hormone mimetic activity. Moreparticularly, it is concerned with straight chain w-monounsaturatedalkenyl, w-haloalkyl, w-hydroxyalkyl, w-epoxyalkyl, w-alkoxyalkyl,w-alkylthioalkyl, w-acylalkyl and wcarbamoylalkyl piperonyl ethers.

Prior art Juvenile hormone is a methyl ester of a multiply unsaturatedbranched chain acid. This branched chain group is made up of isopreneunits characteristic of many natural products. The resulting complexstructure is diflicult to synthesize and is, therefore, not readilyavailable for insect control.

Compounds which functiOn as juvenile hormone insecticides act in adifierent manner on insects than presently used insecticides. Compoundshaving juvenile hormone mimetic activity exert a disrupting influenceupon the normal development of the insects. These compounds interruptthe normal metamorphosis of the pest insects and result in the formationof members of the treated species which develop abnormally and arenonviable or sterile. This ultimately leads, indirectly at least, to thedestruction of the insect population.

DESCRIPTION OF THE INVENTION The compounds of the present invention, ingeneral, possess juvenile hormone mimetic activity. The compounds arestraight chain piperonyl ethers having the following structure (I)wherein R is OH, halogen of atomic number 9 to 35 (fluorine, chlorine orbromine), vinyl, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4carbon atoms, epoxy, acyl of 1 to carbon atoms, carbamoyl singlysubstituted on the nitrogen atom with alkyl groups of l to 4 carbonatoms and n is a whole number of 1 to 14.

Preferably R is hydroxy, chlorine, bromine, vinyl, alkoxy of 1 to 2carbon atoms, alkylthio of 1 to 2 carbon atoms, epoxy, saturated acyl of2 carbon atoms or carbamoyl singly substituted on the nitrogen with amethyl group.

n is preferably a whole number in the range of 2 to 14, more preferably2 to 12 and most preferably 6 to 12.

The acyl groups may be represented by the structure o O-("J-R (II)wherein R is alkyl of 1 to 4 carbon atoms, preferably methyl orcyclopropyl. The carbamoyl group may be represented structurally as OO-il-NHR (III) wherein R is alkyl of 1 to 4 carbon atoms, preferablymethyl.

Still more preferably R is bromine, vinyl or methoxy and n has a valueof 9 to 10.

Representative compounds of the present invention include the following:2 hydroxyethyl piperonyl ether, 4- hydroxybutyl piperonyl ether, 8hydroxyoctyl piperonyl ether, 2 bromoethyl piperonyl ether, 3bromopropyl piperonyl ether, 4 bromobutyl piperonyl ether, S-bromopentylpiperonyl ether, 7 bromoheptyl piperonyl ether, 11 bromoundecylpiperonyl ether, 13 bromotridecyl piperonyl ether, 14 bromotetradecylpiperonyl ether, 12- chlorododecyl piperonyl ether, 9 fluorononylpiperonyl ether, 2 fluoroethyl piperonyl ether, 2 fluoromethyl piperonylether.

Allyl piperonyl ether, B-butenyl piperonyl ether, 4- pentenyl piperonylether, 6 heptenyl piperonyl ether, 10 undecenyl piperonyl ether,ll-dodecenyl piperonyl ether, 12-tridecenyl piperonyl ether.

2 methoxyethyl piperonyl ether, 2 propoxyethyl piperonyl ether, 3propoxypropyl piperonyl ether, 4- ethoxybutyl piperonyl ether, 5ethoxypentyl piperonyl ether, 7 methoxyheptyl piperonyl ether,ll-methoxyundecyl piperonyl ether, 12 methoxy dodecyl piperonyl ether,13 methoxytridecyl piperonyl ether, 9 ethoxynonyl piperonyl ether, 10ethoxydecyl piperonyl ether, 10 butoxydecyl piperonyl ether, 11ethoxyundecyl piperonyl ether, 8 propoxyoctyl piperonyl ether, 9propoxynonyl piperonyl ether, 10 propoxydecyl piperonyl ether, 11propoxyundecyl piperonyl ether, 7 butoxyheptyl piperonyl ether, 9butoxynonyl piperonyl ether, 10-butoxydecyl piperonyl ether.

S-thianonyl piperonyl ether, 9-thiadecyl piperonyl ether, 10 thiaundecylpiperonyl ether, 12 thiatridecyl piperonyl ether, 8 thiadecyl piperonylether, 8 thiaundecyl piperonyl ether, 8 thiadodecyl piperonyl ether,Z-thiapropyl piperonyl ether, 3 thiapentyl piperonyl ether, 3- thiahexylpiperonyl ether.

3,4 epoxybutyl piperonyl ether, 4,5 epoxypentyl piperonyl ether, 5,6epoxyhexyl piperonyl ether, 6,7- epoxyheptyl piperonyl ether, 9,10epoxydecyl piperonyl ether, 10,11-epoxyundecyl piperonyl ether,11,12-epoxydodecyl piperonyl ether, 12,13 epoxytridecyl piperonyl ether,13,14-epoxytetradecyl piperonyl ether.

8 piperonyloxyoctyl acetate, 7 piperonyloxyheptyl acetate, 11piperonyloxyundecyl acetate, 12 piperonyloxydodecyl acetate, 9piperonyloxynonyl propionate, 10- piperonyloxydecyl propionate, 11piperonyloxyundecyl propionate, 9 piperonyloxynonyl butyrate,10-piperonyloxydecyl butyrate, 8 piperonyloxyoctyl butyrate,9-piperonyloxynonyl cyclopropanecarboxylate, IO-piperonyloxydecylcyclopropanecarboxylate, 8-piperonyloxyoctyl cyclopropanecarboxylate, 8piperonyloxyoctyl N methyl carbamate, 11 piperonyloxyundecyl N methylcarbamate, 12 piperonyloxydodecyl N methyl carbamate,13-piperonyloxytridecyl-N-methyl carbamate.

The w-haloalkyl piperonyl ethers of this invention are prepared by thereaction of sodium piperonoxide and an a,w-dibromoalkane as follows:

CH -ONa on, Hal(CHu)u--Hal CH2O(CHz)nHal NaHal CH:

wherein n has the same meaning as before and Hal represents halogen ofatomic number 9 to 35. Other alkali metal salts may be used, e.g.,potassium, lithium, etc.

This reaction (1) is a variation of the well known Williamson ethersynthesis. The dihalide in an equal molar amount is simply added to thesolvent (e.g., dimethoxy ethane, liquid ammonia, tetrahydrofuran,dioxane, etc.) containing the piperonyl salt which is then heated attemperatures in the range of 50 to 150 C. for a period of timesufiicient to carry the reaction to completion about 6 to 24 hours. Thisreaction is conveniently catalyzed by a small amount of iodine. Afterwater washing to remove the by-product salts, crude product is obtainedby evaporation or distillation of the solvent. This crude material maybe used as such or it may be purified by chromatography.

The alkali metal salts of piperonol are readily prepared by the reactionof piperonol with an equal molar amount of sodium hydride, potassiumamide, n-butyl lithium, etc. in an appropriate solvent such as dimethoxyethane, liquid ammonia, tetrahydrofuran, dioxane and the like. Thisreaction is carried out at low temperatures, below about 50 C. Thealkali metal salt is usually prepared in situ and used in the subsequentreaction with an a,w-dihaloalkane without isolation or purification.

The w-unsaturated alkenyl piperonyl ethers of this invention may beprepared by dehydrohalogenation of whaloalkyl piperonyl ethers asillustrated by the reaction below, wherein the halogen is represented asbromine:

+ HBr wherein n is as defined previously.

In this reaction (2) the w-haloalkyl piperonyl ether is heated with anexcess of a strong base in an inert nonaqueous solvent. Solventssuitable for this reaction are preferably high boiling and includedimethoxyethane, dioxane, diethyleneglycol, monoethyl ether ofdiethyleneglycol and the like. Strong bases for this reaction includethe alkali metal hydroxides, e.g. sodium hydroxide, potassium hydroxide,etc. The reaction is carried out at temperatures in excess of 50 0.,preferably at the reflux temperature of the solvent. Reaction times forcompletion depend on the temperature but are generally in the range of 4to 24 hours. The crude product is obtained by evaporating or distillingoff the solvent after it has been washed to remove by-product salts.

The w-unsaturated alkenyl piperonyl ethers of this invention may also beprepared by the reaction of a terminally unsaturated primary alcohol andpiperonyl halide as follows (the halogen is represented by bromine):

This reaction is essentially the same as process 1) described above forthe preparation of w-haloalkyl piperonyl ethers.

The w-alkoxyalkyl piperonyl ethers and the w-alkylthioalkyl piperonylethers are prepared from the corresponding w-haloalkyl piperonyl ethersas follows:

R XNa This reaction is essentially the same as reaction (1) describedabove for the preparation of w-haloalkyl piperonyl ethers and is carriedout in substantially the same manner.

The w-epoxyalkyl piperonyl ethers of this invention are prepared byepoxidizing the terminally unsaturated alkenyl piperonyl ethers, asfollows:

wherein n has the same meaning as before.

Epoxidations are well known reactions of olefins and are effected bycontacting the olefin with an epoxidizing agent such as perbenzoic acid,m-chloroperbenzoic acid, and peracetic acid. The reaction is usuallycarried out in solvents such as chloroform, acetic acid and diethylether, at temperatures below about 25 0., preferably 010 C. Thereactants are mixed slowly and kept in contact at these low temperaturesfor periods of time ranging from 2 hours to 2 or more days. The productis obtained by first washing out the acid by-products with a dilutebasic solution, and then removing the organic solvent by evaporation ordistillation. The crude product obtained in this way may be used as suchor it may be purified by chromatography.

The w-hydroxyalkyl piperonyl ethers are prepared by the reaction ofpiperonyl bromide and a sodium w-hydroxyalkoxide as follows:

This reaction is carried out in a manner substantially the same as thatdescribed above for reaction (3).

The w-acylalkyl piperonyl ethers and the w-carbamoylalkyl piperonylethers are prepared by reacting w-hydroxyalkyl piperonyl ether with asuitable acylchloride or alkyl isocyanate, respectively, according tothe following Equations 7 and 8:

The above reactions are, of course, well known acylation andcarbamoylation reactions. The w-acylalkyl piperonyl ethers may also beprepared by reacting the w-hydroxyalkyl piperonyl ether with ananhydride such as acetic anhydride. This reaction is also well known.

The compounds of the present invention may be more fully understood byreference to the following examples.

Example l.-Preparation of 8-bromooctyl piperonyl ether Piperonol, 15.2g. (0.1 mole), was dissolved in 200 ml. of dimethoxyethane. To thissolution there was added 4.8 g. (0.1 mole) of sodium hydride. Theresulting mixture was refluxed for 30 minutes after which 27.2 g. (0.1mole) of 1,8-dibromooctane and a crystal of iodine were added. Thismixture was then refluxed for 24 hours. At the end of this time, themixture was cooled and mixed with an equal amount of water. Then a likeamount of dichloromethane was added and the two layers were separated.The organic layer was dried and evaporated. The crude product obtainedin this way was purified by passing through a silica gel chromatographycolumn using a 5% ether in hexane eluant. In this way there was obtained13 g. of oily 8-bromooctyl piperonyl ether. The NMR spectra wasconsistent with the assigned structure. An infrared spectra had strongadsorptions at 3.4, 3.5, 6.7, 6.95, 8.0, 9.1, 9.6, 10.7 and 12.3microns. Analysis was as follows:

Br. (percent): Calculated, 23.3; found, 23.3.

Example 2.Preparation of 7-octenyl piperonyl ether A crude 8-bromooctylpiperonyl bromide was prepared by refluxing 15.2 g. (0.1 mole) ofpiperonol, 27.2 g. (0.1 mole) of 1,8-dibromooctane and 13.8 g. (0.1mole) of potassium carbonate in 200 ml. of acetone for 36 hours. At theend of this time the mixture was filtered and evaporated to dryness. Tothis crude product there was added 200 ml. of dimethoxy ethane and 11.2g. (0.2 mole) of potassium hydroxide. The resulting mixture was heatedat reflux for 24 hours, after which the material was cooled, filteredand evaporated to give crude 7-octenyl piperonyl ether. This product waspurified by passing it through a silica gel chromatography column usingpetroleum ether as the eluent. The purified 7-octenyl piperonyl etherwas an oil and weighed 5 g. NMR spectra was consistent with the assignedstructure. Infrared spectra had strong adsorption bands at 3.4, 3.5,6.1, 6.7, 6.95, 8.0, 9.1, 9.6, 10.6, 10.9 and 12.3 microns. Analysis wasas follows:

C (percent): Calculated, 73.3; found, 74.9 H (percent): Calculated, 8.4;found, 8.5

Example 3.Preparation of 8-methoxyoctyl piperonyl ether 8-bromopiperonylether, 19.0 g. (0.55 mole) and 5.6 g. (0.1 mole) of potassium hydroxidewere refluxed in 150 ml. of methanol for 2 hours. After cooling, thereaction mixture was filtered and the filtrate evaporated to give aresidue which was chromatographed through a silica gel column using a 5%ether in hexane eluent to obtain a first fraction and a 20% ether inhexane eluent to obtain a second fraction. The first fraction wasevaporated to give 3 g. of 7-octenyl piperonyl ether, the secondfraction was evaporated to give 8 g. of oily, 8-methoxyoctyl piperonylether. The NMR spectra was consistent with the assigned structure. Aninfrared spectra had strong adsorption peaks at 3.4, 3.5, 6.7, 6.95,8.0, 8.9-9.1, 9.6, 10.6 and 12.3 microns. Analysis was as follows: C(percent): Calculated, 69.4; found, 70.5 H (percent): Calculated, 8.8;found, 9.0

Example 4.--Preparation of IO-undecenyl piperonyl ether (A) Pi-peronylbromide.-Piperonol, 30.4 g. (0.2 mole) was added in small portions to200 ml. of 48% hydrobromic acid at 0 C. When all had been added, thereaction mixture was diluted with 200 ml. of water and stirred for anadditional 30 minutes. Then 200 ml. of dichloromethane was added. Thelayers were separated, the organic layer was washed with water and driedover magnesium sulfate. The solvent was removed by evaporation underreduced pressure to give 38.5 g. of piperonyl bro- ,rnide.

(B) 10-undecenol-1.To a mixture of 7.6 g. (0.2 mole) of lithium aluminumhydride in ml. of ether, there was added over a period of 8 hours, 36.8g. (0.2 mole) of 1-0 undecenoic acid dissolved in 100 ml. of ether. Whenall was added the resulting mixture was refluxed for 1% hours. Theresulting mixture was then added to 200 ml. of 3 N hydrochloric acid.The ether layer was separated, washed with aqueous sodium bicarbonate,and dried over magnesium sulfate. The solvent was removed under vacuumto give a crude product which was washed with aqueous potassiumcarbonate, dissolved in hexane and dried again. Evaporation of thehexane gave 34 g. of lO-undecenol-l.

(C) IO-undecenyl piperonyl ether.Sodium hydride, 4.8 g. (0.1 mole) wasadded to a stirred solution of 7.0 g. (0.1 mole) of IO-undecenol-l in100 ml. of hexane. The resulting mixture was refluxed for 1% hours. Atthe end of this time, 21.5 g. (0.1 mole) of piperonyl bromide dissolvedin 200 ml. of hexane was added and refluxing was continued for 18 hours.Then the reaction mixture was added to 300 ml. of water. The organiclayer was separated and dried. After evaporation of the solvent thecrude product obtained thereby was passed through a silica gelchromatographic column using a 10% ether in hexane eluent. The purifiedll-undecenyl piperonyl ether weighed 17 g. The infrared spectra hadstrong adsorption bands at 3.4, 3.5, 6.1, 6.7, 6.95, 8.0, 9.1, 9.6,10.7, 11.0 and 12.3 microns.

Example 5.-Preparation of 10,11-epoxyundecenyl piperonyl ether To asolution of 11.0 g. (0.036 mole) of l0-undecenyl piperonyl ether and 5.0g. (0.036 mole) of sodium dihydrogen phosphate monohydrate in 100 ml. ofdichloromethane, was added 7.6 g. (0.036 mole) of m-chloroperbenzoic anddissolved in 200 ml. of dichloromethane. After stirring at ambienttemperature for 24 hours, the mixture was filtered and washed with anaqueous sodium bicarbonate solution. After drying the dichloromethanesolvent was removed by evaporation. The crude product obtained in thisway was purified by passing through a silica gel chromatographic columnusing first a 5% ether in hexane eluent and then a 50% ether in hexaneeluent to recover the 10,11-epoxyundecenyl piper- 7 onyl ether whichweighed g. An infrared spectra had strong adsorption peaks at 3.4, 3.5,6.7, 6.95, 7.9-8.0, 9.1, 9.6, 10.8 and 12.4 microns.

Example 6.Preparation of 13-thiatetradecyl piperonyl ether Methylmercaptan, 1.6 g. (0.032 mole) was bubled into a solution of 13.0 g.(0.032 mole) of IZ-bromododecyl piperonyl ether, and 5.6 g. of (0.1mole) of potassium hydroxide in 150 ml. of dimethoxyethane. When all hadbeen added the resulting mixture was heated at reflux for 3 hours. Aftercooling and filtering, the solvent was removed by evaporation. The crudeproduct was then dissolved in hexane and filtered. The filtrate wasevaporated to give 8.5 g. of oily product. The NMR spectra wasconsistent with the assigned structure. The infrared spectra had strongadsorption peaks at 3.4, 3.5, 6.7, 6.95, 8.0, 9.0, 9.6, 10.6 and 12.2microns. Analysis was as follows:

C (percent): Calculated, 68.7; found, 69.5 H (percent): Calculated, 9.3;found, 9.7

Other compounds were prepared from appropriate starting materials usingthe procedures described above. These compounds are given in Table I.

tion of pupa characteristics in the adult. The degree of juvenilizationwas scored by the method of W. S. Bowers and M. J. Thompson (Science142, 1469-70 (1963)). In this method of scoring:

0=normal appearing adult 0.5:essentially normal appearing adult, slighttrace of gin traps 1=slight retention of pupa characteristics4=supernumerary or second pupa, maximum juvenilization.

TABLE I Elemental analysis, percent Melting Calculated Found Examplepoint, number Compound C. C H Br N C H Br N 7 fi-bromohexyl piperonylether Oil 8.- 9-bromononyl piperonyl ether Oil 9 10-bromodecyl piperonylether Oil 1(1) 12-bromododecyl piperonyl ether. 25627 12 Oil 13 Oil 1Oil 15. Oil 16-.-- Oil 17..-. 12-ethoxydodeeyl piperonyl ether Oil18.... ll-methoxyundecyl piperonyl ether Oil 19.--. ll-bromoundecylpiperonyl ether Oil 20. 9-ehlorononyl piperonyl ether- Oil 21hydroxynonyl piperonyl ether 25 69. 4 8. 8 2 IO-hydroxydecyl piperonylether 28 70. 2 9.1 71. 5 9. 4 23. Q-piperonyloxynonyl acetate- 31-82 67.9 8. 3 68. 6 8. 4 24. l0'piperonyloxydecyl acetate Oil 68. 6 8.6 68. 78.8 25.-.- 9-piperonyloxynonyl N-methylcarbamate -51 65.0 8. 3 65. 9 8.226... 10-piperonyloxydeeyl N-methylcarbamate-.. 66-68 65. 7 8. 5 66. 68. 7 27..-- 12-piperonyloxydodecyl acetate 26-27 70. 0 9. 0 69. 2 8.728. 9-piperonyloxynonyl cyclopropanecarboxylate-.. Oil 69. 5 8. 2 65. 67. 9 29. lfl-piperonyloxydecyl cyclopropaneearboxylate. Oil 70. 2 8. 5269. 2 8. 3 30- 12-piperonyloxydodecyl cyclopropanecarboxylate 26 71. 28. 92 70.3 8. 8 31. 12-hydroxydodecylpiperonyl ether. 33 71. 4 9.23 72.4 9.6 32- 10piperonyloxydecyl propionate Oil 69. 3 8. 8 67. 8 8. 8 33IO-piperonyloxydecyl butyrate Oil 70.0 9. 0 67.4 8. 7

1 Chlorine.

The compounds of the present invention are useful as insecticides,particularly as juvenile hormone mimetic insecticides; that is theyinhibit the normal growth pattern of certain insects thereby limitingreproduction of these insects.

The compounds of the present invention were tested as juvenile hormonemimetic insecticides against the following insects: Yellow mealworm (Tenebrio molitor), cabbage looper (Trichoplusia m) and kissing bug(Rhodm'us prolixus).

The test procedures were substantially as follows:

For the yellow mealworm test an acetone solution containing a certainconcentration in micrograms of the test compound in 5 microliters ofsolution was topically applied to the abdomens of the mealworm pupaewhich were less than 48 hours old. Usually 10 pupae were so treated. Thetreated pupae were placed in a Petri dish and placed in an incubator at27 C. in darkness until they emerged (or tried to emerge) about one weekafter treatment. A count was made of the dead. The live specimens wereexamined under a microscope for juvenilization, i.e. retentality of theadults was determined. The degree of juvenilization was measured basedon the following:

0=normal appearing pupa 1= /2 larva-V2 pupa; no prolegs; pupoid thorax2= /z larva- /z pupa; prolegs; pupoid thorax 3=supernumerary larva0:normal adult no effect 1-9=adult with nymph like characteristics11-18=nymph with some adult characteristics 19=supernumerary nymph(sixth stage).

Percent control, based on larva, pupa and adult insect mortalityreadings at each stage are reported in Table II.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed,

TABLE II Yellow mealworm Cabbage looper Kissing bug .Tuvenili- Juvenill-Juvenilization, zstion, zation, Compound Cone, ereent Percent Qono,percent Percent Cnc., percent Percent of Ex. No. g./lnsect degree)control ugJmsect (degree) control rig/insect (degree) control The acylderivatives (wherein R=acyl) of the compounds of the invention,particularly those of structure II wherein R is methyl or cyclopropyl,are also effective as ovicides. For example, IO-piperonyloxydecylcyclopropanecarboxylate and 10-piperonyloxydecyl acetate, were found topossess ovicidal activity against eggs of the two-spotted spider mite(Tetranychus urtica Koch).

When used as an insecticide the compounds may be applied in eitherliquid or solid formulations to the insects, their environment or hostssusceptible to insect attack. For example, they may be sprayed orotherwise applied directly to plants or soil so as to effect control ofinsects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxicamount of one or more of the compounds and a biologically inert carrier.Usually they will also contain a wetting agent. Soild carriers such asclay, talc, sawdust and the like may be used in such formulations.Liquid diluents which may be used with these compounds include water andaromatic solvents. In addition these formulations may contain othercompatible pesticides, fillers, stabilizers, attractants and the like.

The concentration of the active ingredient to be used with inertcarriers, either solid or liquid carriers, will be dependent upon manyfactors, such as the particular compound which is used, the carrier inor upon which it is incorporated, the method and conditions ofapplication, the insect species to be controlled, etc., the properconsideration of these factors being within the skill of those versed inthe art. In general, the toxic ingredients of this invention will beeffective in concentrations from about 0.0001 percent by weight to ashigh as 50 percent by weight or higher. Economically, of course, it isdesirable to use lower concentrations of this active ingredient. Thus,it is usually desirable to use less than 20 percent by weight of theactive ingredient in a particular composition.

The terms insecticide and insect as used herein refer to their broad andcommonly understood usage rather than to those creatures which in thestrict biological sense are classified as insects. Thus, the term insectis used not only to include small invertebrate animals belonging to theclass Insecta but also to other related classes of arthropods whosemembers are segmented invertebrates having more or fewer than six legs,such as spiders, mites, ticks, centipedes, worms and the like.

in the light of the foregoing disclosure and discussion, withoutdeparting from the spirit or scope of the disclosure or from the scopeof the following claims.

I claim:

1. Compound of the formula wherein R is hydroxy, halogen of atomicnumber 9 to 35, vinyl, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to4 carbon atoms, epoxy, acyclic carboxylic acyl of l to 5 carbon atoms orcarbamoyl singly substituted on the nitrogen atom with alkyl of 1 to 4carbon atoms and n is 1 to 14.

2. Compound of claim 1 wherein n is 2 to 14.

3. Compound of claim 1 wherein n is 6 to 12.

4. Compound of claim 1 wherein R is hydroxy, chlorine, bromine, vinyl,alkoxy of l to 2 carbon atoms, alkylthio of 1 to 2 carbon atoms, epoxy,acyclic carboxylic acyl group of 2 carbon atoms or carbamoyl singlysubstituted on the nitrogen atom with methyl.

5. Compound of claim 1 wherein R is bromine, vinyl or methoxy and n is 2to 14.

6. Compound of claim 5 wherein R is bromine and n is 6 to 12.

7. Compound of claim 6 wherein n is 9.

6 8. (llgmpound of claim 5 wherein R is vinyl and n is 9. Compound ofclaim 8 wherein n is 9.

10. Compound of claim 5 wherein R is methoxy and n is 6 to 12.

11. Compound of claim 10 wherein n is 9.

References Cited UNITED STATES PATENTS 2,421,569 6/1947 LaForge et al.260-3405 2,773,062 12/ 1956 Prill 260-340.5 3,070,607 12/ 1962 Barthelet al. 260-3405 3,117,135 1/ 1964 Hedenburg 260-3405 I. H. TURNIPSEED,Assistant Examiner U.S. Cl. X.R. 424282

